EP0835886B1 - Procédé pour la préparation et l'utilisation de composés méso/racémiques du type (bis(indényl)éthane)zirconium-dichloro - Google Patents
Procédé pour la préparation et l'utilisation de composés méso/racémiques du type (bis(indényl)éthane)zirconium-dichloro Download PDFInfo
- Publication number
- EP0835886B1 EP0835886B1 EP96116159A EP96116159A EP0835886B1 EP 0835886 B1 EP0835886 B1 EP 0835886B1 EP 96116159 A EP96116159 A EP 96116159A EP 96116159 A EP96116159 A EP 96116159A EP 0835886 B1 EP0835886 B1 EP 0835886B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- indenyl
- meso
- bis
- ethane
- racemic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title description 4
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical class Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 21
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- WAADRLKGQPOVGL-UHFFFAOYSA-N 1-[1-(1h-inden-1-yl)ethyl]-1h-indene Chemical compound C1=CC2=CC=CC=C2C1C(C)C1C2=CC=CC=C2C=C1 WAADRLKGQPOVGL-UHFFFAOYSA-N 0.000 claims abstract description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 8
- -1 zirconium dichloride compound Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000008247 solid mixture Substances 0.000 claims abstract description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 9
- RYMHWULWPBJOFE-UHFFFAOYSA-L 1-[1-(1h-inden-1-yl)ethyl]-1h-indene;zirconium(2+);dichloride Chemical group [Cl-].[Cl-].[Zr+2].C1=CC2=CC=CC=C2C1C(C)C1C2=CC=CC=C2C=C1 RYMHWULWPBJOFE-UHFFFAOYSA-L 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 239000012429 reaction media Substances 0.000 abstract description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229910007928 ZrCl2 Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CTWJQOQFTNPBCX-UHFFFAOYSA-N 1-[2-(1h-inden-1-yl)ethyl]-1h-indene Chemical compound C1=CC2=CC=CC=C2C1CCC1C2=CC=CC=C2C=C1 CTWJQOQFTNPBCX-UHFFFAOYSA-N 0.000 description 1
- MJHAEXLGDADEGZ-UHFFFAOYSA-N CC(C1C2=CC=CC=C2C=C1)C1C2=CC=CC=C2C=C1.Cl.Cl Chemical group CC(C1C2=CC=CC=C2C=C1)C1C2=CC=CC=C2C=C1.Cl.Cl MJHAEXLGDADEGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
Definitions
- the present invention relates to supported meso/racemic-[bis(indenyl)ethane]zirconium dichloride compounds having a meso/racemic ratio of at least 75/25, their preparation and their use as catalysts in the polymerization or copolymerization of olefins.
- said process is a process for the preparation of a supported meso/racemic [bis(indenyl) ethane] zirconium dichloride compound having a meso/racemic ratio of at least 75/25 comprising:
- This invention relates also to a process for the polymerization or copolymerization of olefins comprising contacting at least one olefinic monomer in the presence as catalyst of a supported meso/racemic-[bis-(indenyl)ethane]zirconium dichloride compound having a meso/racemic ratio of at least 75/25 such as prepared.
- the supported meso/racemic-[bis(indenyl)ethane]ZrCl 2 metallocenes of the invention are obtained by reacting zirconium tetrachloride with the solid reaction product of the bis(indenyl)ethane ligand with an alkyllithium in an ether, preferably diethyl ether, pentane or a mixture thereof, as reaction medium and by recovering a solid mixture of lithium salt and of the meso/racemic compound, the reaction between ZrCl 4 and the above mentioned solid reaction product being conducted under stirring at a temperature from 15 to 30°C, room temperature (about 25°C) being preferred for obvious reasons.
- reaction solvent lowering the temperature will require a longer reaction time, while increasing the temperature may result in a complete evaporation of the reaction solvent.
- duration of reaction is generally between 1 and 3 hours, preferably of the order of about 2 hours.
- the reaction pressure is usually atmospheric.
- dry and oxygen-free conditions are required for this type of reaction and for the storage of the metallocenes.
- the ligand may be prepared by using various methods well known in the art, depending on the selection of the specific substituents.
- the reaction of the ligand with an alkyllithium is also well known in the art ;it is generally carried out by dropwise addition of an alkyllithium solution in a solution of the ligand. Methyllithium and n-butyllithium are most often used, as are stoechiometric ratios of the reactants.
- the solid reaction product may be recovered by complete evaporation of the solvent. During the evaporation conditions, said product may have to be reduced to a fine powder, e.g. by grinding in a mortar.
- reaction solvent is decanted and a solid mixture of lithium chloride and the isomeric metallocene is collected.
- the metallocene is separated from the lithium salt with an extractant solvent.
- Suitable solvents are methylene chloride and dichloromethane.
- the isomeric metallocene catalyst is used in a supported form.
- Suitable supports are silicae having a surface area comprised between 200 and 600 m 2 /g and a pore volume comprised between 0.5 and 4.5 ml/g.
- a process for the polymerization or copolymerization of olefins comprising contacting one or more olefinic monomers such as ethylene or propylene in the presence as catalyst of an isomeric metallocene such as obtained hereinabove.
- racemic isomer may be beneficial to the mechanical and optical properties of the polyethylene or polypropylene film obtained since it would give rise to a high molecular weight tailing in the distribution.
- the process of the present invention can be also extended to other bis(indenyl)ethane)ZrCl 2 complexes with different substituents, in particular those with 2,2'-substituted and 2,2',4,4'-substituted indenyl ligands.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerization Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Claims (12)
- Procédé pour préparer un composé de dichlorure de [bis (indényl) éthane] zirconium méso/racémique sur support ayant un rapport méso/racémique d'au moins 75/25 comprenanta. faire réagir le tétrachlorure de zirconium avec un produit de réaction solide du ligand bis (indényl) éthane avec un alkyllithium dans du diéthyl éther, du pentane ou un mélange de ceux-ci,b. récupérer un mélange solide de chlorure de lithium et une composition méso/racémique de dichlorure de [bis(indényl)éthane] zirconium;c. séparer la composition méso/racémique de dichlorure de bis(indényl)éthane zirconium du dichlorure de lithium au moyen d'un solvant extractant;d. traiter la composition méso/racémique de dichlorure de [bis(indényl)éthane] zirconium obtenue au cours de l'étape (c) avec un solvant extractant;e. mettre sur support la composition méso/racémique de dichlorure de [bis(indényl)éthane] obtenue au cours de l'étape (d).
- Procédé selon la revendication 1 au cours duquel la réaction (a) est mise en oeuvre sous agitation à une température de 15 à 30°C.
- Procédé selon les revendications 1 ou 2 où la durée de cette réaction (a) est entre 1 et 3 heures.
- Procédé selon la revendication 3 où cette durée est de 2 heures.
- Procédé selon l'une quelconque des revendications 1 à 4 où le produit de la réaction du ligand avec l'alkyllithium est ajouté sous forme de poudre.
- Procédé selon l'une quelconque des revendications 1 à 5 où le solvant extractant est le chlorure de méthylène ou le dichlorométhane.
- Procédé selon l'une quelconque des revendications 1 à 6 où le ligand de bis(indényl)éthane est choisi parmi les ligands indényles de 2,2' substitués et de 2,2',4,4' substitués.
- Procédé selon l'une quelconque des revendications 1 à 7 au cours duquel le support est de la silice ayant une aire de surface comprise entre 200 et 600 m2/g et un volume de pores compris entre 0,5 et 4,5 ml/g.
- Un composé de dichlorure de [bis(indényl)éthane] zirconium sur support obtenu par le procédé selon les revendications 1 à 8 caractérisé en ce que le composé a un rapport méso/racémique d'au moins 75/25.
- Procédé de polymérisation ou copolymérisation d'oléfines comprenant la mise en contact d'au moins un monomère oléfinique en présence, comme catalyseur d'un composé tel que celui préparé selon l'une quelconque des revendications 1 à 8.
- Procédé selon la revendication 10 où le monomère oléfinique est de l'éthylène ou le propylène.
- Procédé selon l'une quelconque des revendications 1 à 11, où le support est la silice ayant une aire de surface comprise entre 200 et 600m2/g et un volume de pores compris entre 0,5 et 4,5 ml/g.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE69631659T DE69631659T2 (de) | 1996-10-09 | 1996-10-09 | Verfahren zur Herstellung und Verwendung von meso-racemisch Bis(Indenyl)Ethan-Zirconium-Dichloridverbindungen |
| ES96116159T ES2213761T3 (es) | 1996-10-09 | 1996-10-09 | Proceso de obtencion y utilizacion de compuestos dicloruro de (bis(indenil)etano)circonio meso/racemicos. |
| DK96116159T DK0835886T3 (da) | 1996-10-09 | 1996-10-09 | Fremgangsmåde til fremstilling og anvendelse af meso/racemiske (bis(indenyl)ethan)zirconiumdichloridforbindelser |
| EP96116159A EP0835886B1 (fr) | 1996-10-09 | 1996-10-09 | Procédé pour la préparation et l'utilisation de composés méso/racémiques du type (bis(indényl)éthane)zirconium-dichloro |
| AT96116159T ATE260304T1 (de) | 1996-10-09 | 1996-10-09 | Verfahren zur herstellung und verwendung von meso-racemisch bis(indenyl)ethan-zirconium- dichloridverbindungen |
| PT96116159T PT835886E (pt) | 1996-10-09 | 1996-10-09 | Processo para a preparacao e utilizacao de compostos de dicloreto de (bis(indenil)etano)zirconio meso/racemico |
| JP28626497A JP4115563B2 (ja) | 1996-10-09 | 1997-10-03 | メソ／ラセミ−［ビス（インデニル）エタン］ジルコニウムジクロライド化合物の製造方法および使用 |
| US08/948,224 US6103656A (en) | 1996-10-09 | 1997-10-09 | Process for preparing and using meso/racemic-[bis (indenyl) ethane]zirconium dichloride compounds |
| US10/127,090 US20020115801A1 (en) | 1996-10-09 | 2002-04-22 | Process for preparing and using meso/racemic-[bis (indenyl) ethane] zirconium dichloride compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96116159A EP0835886B1 (fr) | 1996-10-09 | 1996-10-09 | Procédé pour la préparation et l'utilisation de composés méso/racémiques du type (bis(indényl)éthane)zirconium-dichloro |
| US08/948,224 US6103656A (en) | 1996-10-09 | 1997-10-09 | Process for preparing and using meso/racemic-[bis (indenyl) ethane]zirconium dichloride compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0835886A1 EP0835886A1 (fr) | 1998-04-15 |
| EP0835886B1 true EP0835886B1 (fr) | 2004-02-25 |
Family
ID=26142231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96116159A Expired - Lifetime EP0835886B1 (fr) | 1996-10-09 | 1996-10-09 | Procédé pour la préparation et l'utilisation de composés méso/racémiques du type (bis(indényl)éthane)zirconium-dichloro |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US6103656A (fr) |
| EP (1) | EP0835886B1 (fr) |
| JP (1) | JP4115563B2 (fr) |
| AT (1) | ATE260304T1 (fr) |
| DE (1) | DE69631659T2 (fr) |
| DK (1) | DK0835886T3 (fr) |
| ES (1) | ES2213761T3 (fr) |
| PT (1) | PT835886E (fr) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0953582A1 (fr) * | 1998-04-27 | 1999-11-03 | Fina Research S.A. | Production de polyoléfine |
| KR100709557B1 (ko) * | 2007-01-02 | 2007-04-20 | 한국과학기술연구원 | 입상 지르코늄 나노 메조구조체의 제조방법 |
| US9376518B2 (en) | 2013-08-28 | 2016-06-28 | Exxonmobil Chemical Patents Inc. | Racemo selective metallation process |
| SG11201508765TA (en) * | 2013-08-28 | 2015-11-27 | Exxonmobil Chem Patents Inc | Racemo selective metallation process |
| BR122020005071B1 (pt) * | 2014-02-11 | 2021-06-08 | Univation Technologies, Llc | composição de catalisador |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3742934A1 (de) * | 1987-12-18 | 1989-06-29 | Hoechst Ag | Verfahren zur herstellung einer chiralen, stereorigiden metallocen-verbindung |
| US5017714A (en) * | 1988-03-21 | 1991-05-21 | Exxon Chemical Patents Inc. | Silicon-bridged transition metal compounds |
| EP0426643B1 (fr) * | 1989-10-30 | 1995-12-27 | Fina Research S.A. | Procédé de préparation de métallocènes |
| US5117020A (en) * | 1989-10-30 | 1992-05-26 | Fina Research, S.A. | Process for the preparation of metallocenes |
| NL9101502A (nl) * | 1991-09-06 | 1993-04-01 | Dsm Nv | Werkwijze voor het bereiden van een gebrugde metalloceenverbinding alsmede een katalysatorcomponent en een werkwijze voor de polymerisatie van een olefinen. |
| DE69224184T2 (de) * | 1992-06-13 | 1999-06-02 | Targor GmbH, 55116 Mainz | Verfahren zur Herstellung von verbrückten, chiralen Metallocenkatalysatoren des Types Bisindenyl |
| KR100280253B1 (ko) * | 1992-06-18 | 2001-02-01 | 간디 지오프레이 에이치. | 에틸렌 중합체의 제조방법 |
| TW294669B (fr) * | 1992-06-27 | 1997-01-01 | Hoechst Ag | |
| IT1273661B (it) * | 1994-07-20 | 1997-07-09 | Spherilene Srl | Catalizzatori per la polimerizzazione delle olefine |
| AU4527196A (en) * | 1994-12-21 | 1996-07-10 | Exxon Chemical Patents Inc. | A method of preparing high purity racemic metallocene alkyls and use thereof |
| US5556997A (en) * | 1995-04-24 | 1996-09-17 | Albemarle Corporation | Enhanced synthesis of racemic metallocenes |
-
1996
- 1996-10-09 EP EP96116159A patent/EP0835886B1/fr not_active Expired - Lifetime
- 1996-10-09 PT PT96116159T patent/PT835886E/pt unknown
- 1996-10-09 DK DK96116159T patent/DK0835886T3/da active
- 1996-10-09 AT AT96116159T patent/ATE260304T1/de not_active IP Right Cessation
- 1996-10-09 DE DE69631659T patent/DE69631659T2/de not_active Expired - Lifetime
- 1996-10-09 ES ES96116159T patent/ES2213761T3/es not_active Expired - Lifetime
-
1997
- 1997-10-03 JP JP28626497A patent/JP4115563B2/ja not_active Expired - Fee Related
- 1997-10-09 US US08/948,224 patent/US6103656A/en not_active Expired - Lifetime
-
2002
- 2002-04-22 US US10/127,090 patent/US20020115801A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ES2213761T3 (es) | 2004-09-01 |
| EP0835886A1 (fr) | 1998-04-15 |
| DE69631659T2 (de) | 2004-12-23 |
| US6103656A (en) | 2000-08-15 |
| DK0835886T3 (da) | 2004-05-17 |
| JPH10130322A (ja) | 1998-05-19 |
| PT835886E (pt) | 2004-05-31 |
| ATE260304T1 (de) | 2004-03-15 |
| JP4115563B2 (ja) | 2008-07-09 |
| US20020115801A1 (en) | 2002-08-22 |
| DE69631659D1 (de) | 2004-04-01 |
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